Cellulose acetate fibers containing nickel carbonate



United States Patent CELLULOSE ACETATE FIBERS CONTAINING NICKEL CARBONATE Application January 30,1957

5 Claims. (Cl. 106-494) No Drawing.

This invention relates to cellulose acetate fibers of improved dyeing properties and to a method of producing said fibers. In a specific aspect this invention relates to cellulose acetate fibers containing a nickel salt of an organic acid, said fibers being capable of dyeing with a metallizable dye.

It is known in the art that compounds of metals such as nickel, chromium, cobalt and the like, react with certain dyes to produce stable colored metal complexes known as metallized dyes. Such dyes have been employed in the dyeing of cellulose acetate fibers. The metallized dye can be prepared by reacting the non-metallized dye with a suitable metal salt and the resulting metalliz ed dye can then be used for dyeing cellulose acetate fibers. Alternatively, the cellulose acetate fibers can be dyed with the non-metallized dye and metallization of the dye can be effected on the fiber by reaction "with a suitable metal salt. In either event, metallization of the dye is effected in a separate step or operation.

It is an object of this invention to provide a method for dyeing cellulose acetate fibers with non-metallized dyes wherein metallization of the dye is effected during the dyeing operation and without the necessity of a separate metallization step in the process. It is a further object of this invention to provide cellulose acetate fibers containing a metal salt such that during the dyeing of the fiber with a non-metallized dye, metallization of the dye 'is actually carried out.

In accordance with this invention, it has been found that addition of nickel carbonate to the cellulose acetate prior to dyeing of the cellulose acetate with a non-metallized metallizable dye makes it possible to dye the cellulose fiber and at the same time efiect metallization of the dye on the fiber. The presence of the nickel carbonate on the cellulose acetate fiber presents several advantages. .For example, the nickel carbonate causes no deacetylation of the cellulose acetate similar to that which can result when other metallic salts are used. Secondly, the low molecular weight of the nickel carbonate permits the introduction of a suificient amount of metal into the fiber to elfect metallization of the dye with a minimum of color being obtained from the nickel carbonate. Also the use of nickel carbonate makes it unnecessary to load up the fiber with sutficient foreign material to cause deterioration of the textile properties of the garment or fabric.

In practicing this invention, nickel carbonate is .added 2,882,176 Patented Apr. 14, 1959 ice suitable solvent and nickel carbonate added to the solution prior to the spinning of the fiber.

An important feature of this invention is the use of a finely-divided pigment as a support for the nickel carbonate. Actually, the nickel carbonate can be used alone in practicing this invention, but good results can also be obtained when the nickel carbonate is deposited on a fine pigment that has an active surface or a porous structure prior to addition and incorporation in the cellulose acetate. The pigment prevents coagulation of the nickel carbonate during the processing of the cellulose acetate and it also tends to increase the exposed area of the nickel carbonate. In general, the pigment should have a particle size less than about 3 microns and preferably less than 0.5 micron. Suitable pigments thatcan be used are silica gel, activated alumina, ultra-fine calcium carbonate, magnesium carbonate, magnesium oxide, calcium silicate and magnesium silicate. The ultra-fine precipitated calcium carbonates are particularly suitable for use in practicing this invention.

Prior to incorporating the nickel carbonate in the cellulose acetate, it is preferable to grind the nickel carbonate to the desired particle size. The grinding or milling of the nickel carbonate can be carried out either with or without water and if any pigment, such as calcium carbonate, is employed, the pigment can be ground or milled along with the nickel carbonate. After grinding, the nickel carbonate can then be dried by suitable heating and it is ready for addition to the cellulose acetate. The amount of nickel carbonate that is employed is ordinarily within the range of 0.2 to 5 percent by weight of the cellulose acetate, preferably from 0.5 to 2 percent by weight.

After grinding, thenickel carbonate can be added to the cellulose acetate in accordance with this invention and in some instances, it may be found desirable to grind the mixture of nickel carbonate and cellulose acetate. The resulting intimate mixture can then be spun into fiber by a melt-spinning procedure or the mixture can be incorporated into a solvent and spun into a fiber from the resulting dope. In some instances, it may be desirable to incorporate a relatively high percentage of the nickel carbonate into the cellulose acetate and the resulting mixture can then serve as a concentrate or stock which can be diluted subsequently with additional cellulose acetate to obtain any desired concentration of nickel carbonate in the cellulose acetate.

The cellulose acetate that is employed to practice this invention can be prepared by any of the known procedures. For example, cellulose in the form of purified chemical cotton or wood pulp can be given a preliminary treatment with acetic acid. The mass of cellulose wet with acetic acid is then mixed with measured proportions of acetic anhydride catalyst, such as sulfuric acid, and solvent, such as methylene chloride. The resulting mixture is then agitated with suitable temperature control 7 and the acetylating reaction converts the fibrous cellulose to a clear solution of cellulose triacetate. If desired, the cellulose triacetate can be recovered and employed in practicing this invention. However, many types of .cellulose acetate are not in the triester form and the desired degree of acetylation is reached by a hydrolysis reaction induced by adding water and hydrolyzing agent to the triacetate dope with agitation and treatment to drive the reaction to the stage desired. The catalyst is then removed and the charge is precipitated into water followed by thorough purification procedures. The purified cellulose acetate is then dewatered and dried, placing it in a form useful for the practice of this-invention.

The cellulose acetate employed in this invention can have a degree of acetylation ranging from about 50 permeasured by the time of fall of a steel ball through 10 inches of a 20 percent by weight solution of cellulose 'ggetzztze dissolved 'a"9'0':'-l0 aeeto'neiethanol'solution-at The cellulose-acetate containing nickel carbonate prepared in accordance with this invention can be employed to manufacture fibers or yarn in accordance with any of the -lmown procedures. "One of the more common methods for preparingcellulose acetate fibers or yarn involves ,a dry spinning process using an acetone solution. Concen- -ft'rated acetone solutions of cellulose acetate are forced -through spinnerets to form filaments which are cured by "circulated air. T he filaments or fibers are then-gathered and passed over guide rolls to apply controlled twisting and stretching." I If desired, a wet spinning procedure "can also --be risedto" form-the cellulose acetate fibers. or

filair'ients'lln s'uch a: process, the cellulose acetate conta'ining nickel carbonate is dissolved in either'acetic-acid '"or; chloroform"solutions and spun into-a precipitating "liquid. Alternati'v'e'ly,-a melt-spinning procedure can be used a'n'd in-s'uch a'ip'roces's the cellulose acetate is heated to a molten form and spun at therelativel'y high-temperatu're into the "desired filaments. The lower acetyl f forms'of cellulose acetate are more readily soluble in 'the common solvents-and for that reason. are quite adapt- "able to' the-wet 'and dryspinning procedures. The higher ifie'eiyl types'of cellulose acetate are comparatively insoluble in the more common solvents and for that reason -this 'formof cellulose acetate does not lend itself to use akin the wet-and dry spinningprocesses. w

After being spu'n'gthe' cellulose acetatefiber or filadnent containing nickel-carbonate can be easily dyed 1 w-ith-any of the dyes known'to chelate or mordant with 35 "nickel. Among the dyes that canvbe used are those described in U. S. Patents 2,641,602 and 2,651,641. dyes have the'structural formulas:

" no 0 on wherein R is a phenylethyl alcohol nucleus, and

:, wherein A is a monocyclic benzene nucleus containing a CHOE group wherein R represents hydrogen, methyl or ethyl. The above dyes are representative of the compounds "that can be used to chelate with the nickel carbonate in 1 the cellulose 'acetate fibers of this invention. Other suit {able dyes are described in the following copending appli cations:

assava w, I

that employed by those skilled this art heretofore.

anus-kn ji s iwas k wur d a then yedii ast us hsf lighfland-wash fastness;

Straley and Fisher, Serial No. 458,262, filed 24,1954 Straley and Giles, Serial No. 466,955, filed November 4, 1954 Straley and Wallace, Serial No. 498,112, filed March {Ihose dyes known tochelate with nickel are employed to "color cellulose acetate fibers in a'manner similar to v Example 1- I 50 g. of nickel carbonate and 10,000 3. din 5" percent solution of cellulose acetate in acetone are ground for 2.5 hours in a Szegvari 'Attrito'r. The resulting dope,

filtered from the balls used, is adjusted with acetone and cellulose acetate to a dope suitable for spinning and containing 2,450 g. total of cellulose acetate. This dope is tha -sweets. f mes-1 tte'd from the mmnarea gfih-ng- 4 percent with'the' dye "having the formula ,1. 632'. .i' 1 3 011" no. C. JThere resuIted a beautiful dyeing of also-1' goo .w ai v v ;r r 1. In a process for producing a cellulose-acetatefiber capable of being colored with a metallizable' dyea thp improvement which comprises incorporating nearest- ,bonate in the cellulose acetate from which the fiber is formed in an amount within the range of 0.2 to 5 percent by weightof the cellulose acetate prior to formation of said fiber. 2

2. A process according to claim 1 wherein the nickel carbonate is incorporated in an amount within the page of.0.5 to 2 percent by weight of the celluloseacetate.

3. A process according to claim 1 wherein the nick'cl carbonate is incorporated in the solution containing'tiie cellulose acetatefrom which the fiber is formed.

4. As a new composition of matter, a cellulose Izicetatc fiber capable of being colored with-a meta'llizable dye,

said fiber containing from 0.2 to, 5 percent weight of nickel carbonate. p 4 5. As a new composition of matter, acellulose acetate nickel carbonate. a

References Cited in the file of this patent I, UNITED STATES PATENTS Rivat etval. Aug. 16, 1932 2,052,557 Dreyfus Sept. 1, 1936 2,052,558,. Dreyfus Sept. 1, 1936 2,206,278 Dreyfus IulyZ, 1940 FOREIGN PATENTS g Great Britain Nev." 19.."151 9 for UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Potent 2,882,176 I April 14, 1959 Tamas Mn Str'aley et a1.

It 'iioreby certified that error appears. in the printed specification of. the above; numtere. patent requiring corrootion and that the said Letters Patent silioulfi road as, balowo 5301mm 3, lines 44 45,- lowor leftaand portion of the formula,

read i10 Attest:

KARL 331 A'PCLINE ROBERT C WATSON Attesting Officer Conznissioner of Patents 

1. IN A PROCESS FOR PRODUCING A CELLULOSE ACETATE FIBER CAPABLE OF BEING COLORED WITH A METALLIZABLE DYE, THE IMPROVEMENT WHICH COMPRISES INCORPORTING NICKEL CARBONATE IN THE CELLULOSE ACETATE FROM WHICH THE FIBER IS FORMED IN AN AMOUNT WITHIN THE RANGE OF 0.2 TO 5 PERCENT BY WEIGHT OF THE CELLULOSE ACETATE PRIOR TO FORMATION OF SAID FIBER. 